US1844475A - Method of preventing corrosion in oil cracking systems - Google Patents

Method of preventing corrosion in oil cracking systems Download PDF

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Publication number
US1844475A
US1844475A US122743A US12274326A US1844475A US 1844475 A US1844475 A US 1844475A US 122743 A US122743 A US 122743A US 12274326 A US12274326 A US 12274326A US 1844475 A US1844475 A US 1844475A
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United States
Prior art keywords
caustic
ammonia
oil
dephlegmator
solution
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Expired - Lifetime
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US122743A
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Jacque C Morrell
Lyman C Huff
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Universal Oil Products Co
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Universal Oil Products Co
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Publication date
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Priority to US122743A priority Critical patent/US1844475A/en
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/06Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G19/00Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/02Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions

Definitions

  • This invention relates to improvements in a method of preventing corrosion in oil cracking systems, and refers more particularly to the idea of introducing caustic in solution either alone or in combination with ammonia.
  • the specific points and methods cf introducing the caustic, or caustic saturated with ammonia, will be subsequently described.
  • caustic both caustic and ammonia may be used beneficially to materially decrease the amount of corrosion in an 011 crackin system.
  • Caustic of course, being relative y cheaper than ammonia, would be preferable except that it possesses the disadvanta e for this particular use of not being volati c.
  • ammonia is volatile and more reactive, but at the same time is relatively more expensive.
  • caustic will function admirably to decrease the extent of corrosion, while at other times a mixture of caustic and ammonia will function more advantageously.
  • This invention in its broader aspects contemplates the use, therefore, of caustic alone or in combination with ammonia.
  • a caustic solution may be introduced ,to the dephlegmator of an oil cracking apparatus. Instead of being introduced separately, it may be mixed with part of the charging stock being introduced to said dephlegmator. While some of the water containing the caustic may evaporate upon the dephlegmator pans, observation has shown that sus pended particles of caustic will reach the heating coil and eventually be deposited in the reaction chamber. Hence a certain amount of protection against corrosion owing to reaction with corrosive gases formed during the cracking process, such as hydrogen sulphide, will be afiorded by the caustic.
  • the protection to the vapor zones, such as the upper part of the reaction chamber, the vapor line leading from the reaction chamstances formed u her, and the vapor lines leading from the dephlegmator to the condenser, including the condenser, will be limited to that extent which the caustic removes the corrosive subto and through the heating coil.
  • the intro uction of ammonia into the caustic solution introduced into the dephlegmator will give protection to the va or line leading from the dephlegmator an ,to the condenser owing to the fact that ammonia is a volatile substance and reacts very readily with corrosive gases such as the hydrogen sulphide formed during the cracking reaction.
  • a solution of caustic containing ammonia may also be introduced directl into the heating coil, the caustic functionmg to protect in part the heating coil, while the ammonia not only assists in protecting the heating coil but functions also in protecting any vapor spaces within the heating coil.
  • the ammonia will protect by neutralization of the corrosive gases the vapor zones in the reaction chamber and beyond to the dephlegmator, which includes the vapor line leading from the reaction chamber to the dephlegmator. Hence the mixture gives complete protection to the cracking system. It is obvlous that the stream of caustic containing ammonia can be split so that part of the solution may be introduced into the dephlegmator and part into the heating coil.
  • caustic alone may be introduced into the dephlegmator and ammonia alone or in combination with caustic may be introduced into the heating coil.
  • solution of caustic containing ammonia may be mixed with oil being charged into the system in the same manner as caustic alone may be mixed.
  • a cracking apparatus of the tube and drum type comprising generally a heat-ing coil, an enlarged expansion chamber receiving the heated oil therefrom, a dephlegmator communicating with the vapor space of said expansion chamber and a condenser communieating with the upper portion of the dephlegmator.
  • the present method is adapted for use with any type of oil cracking apparatus where corrosion might take place.
  • the reason why the vapor space of the expansion chamber and the vapor line leading therefrom to the dephlegmator will be subjected to the action of a corrosive preventing material is that the ammonia when used, being volatile, will immediately mingle with the vapors and be carried therewith and, in addition, the major portion of the reaction takes place in the reaction chamber.
  • anhydrous or gaseous ammonia maybe utilized, as well asammonia in solution.
  • the caustic used may include sodium hydroxide, soda ash, and even such substances having alkaline reaction like sodium carbonate is contemplated as coming under the broad scope of the invention.
  • a California charging stoc to contain 1 to 1 A;% sulphur, and further assume that it is desired to protect the crack ing system from the corrosion resulting from the cracking of this oil; the caustic and ammonia may be used in combination.
  • a solution of caustic containing 20% of caustic by weight, more or less, is prepared and saturated with ammonia. Approximately an equal weight of ammonia may be dissolved in this solution or in somewhat less concentrated solutions. The total amount of the solution of caustic containing ammonia is so regulated that approximately one pound per barrel of charging oil of caustic and ammonia combined is fed into the cracking system.
  • the relative amounts of caustic and ammonia in the solution may be shifted, depending upon conditions.
  • the solution may contain 15% of caustic and 20% of ammonia and the amount of solution used may be so regulated that approximately one pound of the dissolved substances per barrel of oil charged into the system may be used.
  • a method for preventing corrosion in an oil cracking apparatus of the tube and drum type comprising introducing a solution contaming caustic alkali to the heating coil with the liquid oil and also introducing a solution containing ammonia into the dephlegmator of the oil cracking apparatus whereby the caustic alkali prevents corrosion in that zone of the apparatus occupied by liquid oil and the ammonia prevents corrosion of that zone of the apparatus occupied by the vapors.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

wan.
dill
Patented Feb. 9, 1932 I UNITED STATES .TAOQUE C. IOBBELL'AND Lmll' C. RUFF, 01'
PATENT OFFICE CHICAGO, ILLINOIS, ASSIGNOBS 'IO UNI- VEBKAL OIL PRODUCTS COMPANY, OI CHICAGO, ILLINOIS, A OOBPORATION OF SOUTH DAKOTA METHOD OF PREVENTING CORROSION IN OIL CRACKING SYSTEMS Io Drawing. Application fled Julyv 15, 1928, Serial No. 188,743. Renewed. February 28, 1829.
This invention relates to improvements in a method of preventing corrosion in oil cracking systems, and refers more particularly to the idea of introducing caustic in solution either alone or in combination with ammonia. The specific points and methods cf introducing the caustic, or caustic saturated with ammonia, will be subsequently described.
ltt is well known that both caustic and ammonia may be used beneficially to materially decrease the amount of corrosion in an 011 crackin system. Caustic, of course, being relative y cheaper than ammonia, would be preferable except that it possesses the disadvanta e for this particular use of not being volati c. On the other hand, ammonia is volatile and more reactive, but at the same time is relatively more expensive. For some purposes, therefore, caustic will function admirably to decrease the extent of corrosion, while at other times a mixture of caustic and ammonia will function more advantageously. This invention in its broader aspects contemplates the use, therefore, of caustic alone or in combination with ammonia.
At the present time corrosion is a very vital problem to the owner of an oil cracking systern. The utilization of the present invention., therefore, will be obvious.
The following may be illustrative of the present invention.
A caustic solution may be introduced ,to the dephlegmator of an oil cracking apparatus. Instead of being introduced separately, it may be mixed with part of the charging stock being introduced to said dephlegmator. While some of the water containing the caustic may evaporate upon the dephlegmator pans, observation has shown that sus pended particles of caustic will reach the heating coil and eventually be deposited in the reaction chamber. Hence a certain amount of protection against corrosion owing to reaction with corrosive gases formed during the cracking process, such as hydrogen sulphide, will be afiorded by the caustic.
The protection to the vapor zones, such as the upper part of the reaction chamber, the vapor line leading from the reaction chamstances formed u her, and the vapor lines leading from the dephlegmator to the condenser, including the condenser, will be limited to that extent which the caustic removes the corrosive subto and through the heating coil. The intro uction of ammonia into the caustic solution introduced into the dephlegmator will give protection to the va or line leading from the dephlegmator an ,to the condenser owing to the fact that ammonia is a volatile substance and reacts very readily with corrosive gases such as the hydrogen sulphide formed during the cracking reaction.
A solution of caustic containing ammonia may also be introduced directl into the heating coil, the caustic functionmg to protect in part the heating coil, while the ammonia not only assists in protecting the heating coil but functions also in protecting any vapor spaces within the heating coil. In addition, the ammonia will protect by neutralization of the corrosive gases the vapor zones in the reaction chamber and beyond to the dephlegmator, which includes the vapor line leading from the reaction chamber to the dephlegmator. Hence the mixture gives complete protection to the cracking system. It is obvlous that the stream of caustic containing ammonia can be split so that part of the solution may be introduced into the dephlegmator and part into the heating coil. It is also obvious that caustic alone may be introduced into the dephlegmator and ammonia alone or in combination with caustic may be introduced into the heating coil. Further, the solution of caustic containing ammonia may be mixed with oil being charged into the system in the same manner as caustic alone may be mixed.
The foregoing description has been applied to a cracking apparatus of the tube and drum type, comprising generally a heat-ing coil, an enlarged expansion chamber receiving the heated oil therefrom, a dephlegmator communicating with the vapor space of said expansion chamber and a condenser communieating with the upper portion of the dephlegmator.
It is to be understood that the present method is adapted for use with any type of oil cracking apparatus where corrosion might take place. The reason why the vapor space of the expansion chamber and the vapor line leading therefrom to the dephlegmator will be subjected to the action of a corrosive preventing material is that the ammonia when used, being volatile, will immediately mingle with the vapors and be carried therewith and, in addition, the major portion of the reaction takes place in the reaction chamber.
It is to be noted that anhydrous or gaseous ammonia maybe utilized, as well asammonia in solution. The caustic used may include sodium hydroxide, soda ash, and even such substances having alkaline reaction like sodium carbonate is contemplated as coming under the broad scope of the invention. As an illustration of the proportions which may be used, assume a California charging stoc to contain 1 to 1 A;% sulphur, and further assume that it is desired to protect the crack ing system from the corrosion resulting from the cracking of this oil; the caustic and ammonia may be used in combination.
For the amount of corrosive vapors which will be formed from the commercial cracking of this oil, one pound per barrel of ammonia or caustic will give sufficient protection in their respective zones to cut down the corrosion very substantially and effect a great saving in replacement and elimination of danger from the weakening of the system. A solution of caustic containing 20% of caustic by weight, more or less, is prepared and saturated with ammonia. Approximately an equal weight of ammonia may be dissolved in this solution or in somewhat less concentrated solutions. The total amount of the solution of caustic containing ammonia is so regulated that approximately one pound per barrel of charging oil of caustic and ammonia combined is fed into the cracking system.
It is understood that the relative amounts of caustic and ammonia in the solution may be shifted, depending upon conditions. For example, the solution may contain 15% of caustic and 20% of ammonia and the amount of solution used may be so regulated that approximately one pound of the dissolved substances per barrel of oil charged into the system may be used.
It is appreciated that the larger the amounts of these materials charged into the system with the oil, the greater the protection. Hence theabove example is relative, and smaller amounts may be used with good results at reduced cost.
'VVe claim as our invention:
1. A method for preventing corrosion in an oil cracking apparatus of the tube and drum type comprising introducing a solution contaming caustic alkali to the heating coil with the liquid oil and also introducing a solution containing ammonia into the dephlegmator of the oil cracking apparatus whereby the caustic alkali prevents corrosion in that zone of the apparatus occupied by liquid oil and the ammonia prevents corrosion of that zone of the apparatus occupied by the vapors.
2. A method for preventing corrosion of an ing oil.
JACQUE C. MORRELL. LYMAN C. HUFF.
US122743A 1926-07-15 1926-07-15 Method of preventing corrosion in oil cracking systems Expired - Lifetime US1844475A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2486379A (en) * 1946-07-22 1949-11-01 Dow Chemical Co Manufacture of nuclear halogenated alkenyl-benzene compounds
US2589114A (en) * 1950-01-10 1952-03-11 Pure Oil Co Prevention of ammonium sulfide corrosion
US2755166A (en) * 1951-12-22 1956-07-17 Pure Oil Co Method of reducing vapor zone corrosion
US2757066A (en) * 1952-09-17 1956-07-31 Exxon Research Engineering Co Corrosion prevention
US2780583A (en) * 1954-10-25 1957-02-05 Shell Dev Prevention of hydrogen blistering and fissuring
US2911351A (en) * 1955-09-30 1959-11-03 American Oil Co Corrosion inhibition in condensing exchangers
US3132085A (en) * 1960-09-22 1964-05-05 Gulf Research Development Co Process for reducing formation of carbonaceous deposits on heat transfer surfaces
US3272736A (en) * 1964-07-23 1966-09-13 Exxon Research Engineering Co Method of preventing corrosion
WO2000001785A1 (en) * 1998-07-01 2000-01-13 Betzdearborn Inc. Methods and compositions for inhibiting corrosion

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2486379A (en) * 1946-07-22 1949-11-01 Dow Chemical Co Manufacture of nuclear halogenated alkenyl-benzene compounds
US2589114A (en) * 1950-01-10 1952-03-11 Pure Oil Co Prevention of ammonium sulfide corrosion
US2755166A (en) * 1951-12-22 1956-07-17 Pure Oil Co Method of reducing vapor zone corrosion
US2757066A (en) * 1952-09-17 1956-07-31 Exxon Research Engineering Co Corrosion prevention
US2780583A (en) * 1954-10-25 1957-02-05 Shell Dev Prevention of hydrogen blistering and fissuring
US2911351A (en) * 1955-09-30 1959-11-03 American Oil Co Corrosion inhibition in condensing exchangers
US3132085A (en) * 1960-09-22 1964-05-05 Gulf Research Development Co Process for reducing formation of carbonaceous deposits on heat transfer surfaces
US3272736A (en) * 1964-07-23 1966-09-13 Exxon Research Engineering Co Method of preventing corrosion
WO2000001785A1 (en) * 1998-07-01 2000-01-13 Betzdearborn Inc. Methods and compositions for inhibiting corrosion
US6103100A (en) * 1998-07-01 2000-08-15 Betzdearborn Inc. Methods for inhibiting corrosion

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